Methyl hydrazidodicarboxylate → Bis(1-methoxy-2,2,6,6-tetramethylpiperidin-4-yl) Hydrazine-1,2-dicarboxylate

HRID 1902129Notes

Reaction equation

HRID 1902129 reaction equation
[CH3:1][O:2][N:3]1[C:8]([CH3:10])([CH3:9])[CH2:7][CH:6]([OH:11])[CH2:5][C:4]1([CH3:13])[CH3:12].[NH:14]([C:20]([O:22]C)=O)[NH:15][C:16]([O:18][CH3:19])=[O:17]>CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].[Ti+4]>[NH:15]([C:16]([O:18][CH:19]1[CH2:10][C:8]([CH3:9])([CH3:7])[N:3]([O:2][CH3:1])[C:4]([CH3:13])([CH3:12])[CH2:5]1)=[O:17])[NH:14][C:20]([O:11][CH:6]1[CH2:7][C:8]([CH3:9])([CH3:10])[N:3]([O:2][CH3:1])[C:4]([CH3:13])([CH3:12])[CH2:5]1)=[O:22]

Participants

4

Reactant 2

HCID 265934Methyl hydrazidodicarboxylateHCID 109977701-Methoxy-2,2,6,6-tetramethyl-piperidin-4-ol

Product 1

HCID 54536773Bis(1-methoxy-2,2,6,6-tetramethylpiperidin-4-yl) Hydrazine-1,2-dicarboxylateYield 64%

Reagents, catalysts & solvents 1

HCID 21801Titanium tetrabutoxideCatalyst

Procedure

To a mixture of 15.8 g of 1-methoxy-2,2,6,6-tetramethylpiperidin-4-ol and 5.9 g of dimethyl hydrazine-1,2-dicarboxylate is added 1.4 g of tetrabutyl titanate at room temperature. The mixture is heated at 135°-145° C. for 12 hours and methanol is collected in a Dean-Stark trap. The reaction mixture is partitioned between toluene and water. The organic phase is then washed with water, brine, dried over anhydrous sodium sulfate and evaporated to leave 19.1 g of the crude desired product. Recrystallization of the crude product from acetonitrile affords 11.7 g of the title compound as an off-white solid; mp 147°-149° C.

Workup

  1. temperatureThe mixture is heated at 135°-145° C. for 12 hours
  2. custommethanol is collected in a Dean-Stark trap
  3. customThe reaction mixture is partitioned between toluene and water
  4. washThe organic phase is then washed with water, brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. customevaporated
  7. customto leave 19.1 g of the crude desired product
  8. customRecrystallization of the crude product from acetonitrile

Sources & evidence

ORD record
ord-7b39056e516b41fd8ba659cfb796d433
Source dataset
uspto-grants-1996_11
Patent number
US05578731

Reaction notes

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